Di­chlorido­(4-methyl­aniline-κN)[N-(4-methyl­phen­yl)-1-(thio­phen-2-yl)methanimine-κN]palladium(II)

Butcher, R.J.; Singh, P.; Shabbani, G.

doi:10.1107/S2056989022004960

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ISSN: 2056-9890

Volume 78| Part 6| June 2022| Pages 629-632

https://doi.org/10.1107/S2056989022004960

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Dichlorido(4-methylaniline-κN)[N-(4-methylphenyl)-1-(thiophen-2-yl)methanimine-κN]palladium(II)

Ray J. Butcher,^a ^* Puspendra Singh ^b and Gulam Shabbani ^b

^aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^bDepartment of Chemistry, Dr. Shakuntala Misra National Rehabilitation University, Lucknow, Uttar Pradesh 226017, India
^*Correspondence e-mail: rbutcher99@yahoo.com

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 19 April 2022; accepted 9 May 2022; online 17 May 2022)

The structure of a mono-amine Pd^II complex, [PdCl₂(C₇H₉N)(C₁₂H₁₁NS)], which crystallizes in the triclinic space group, P $[\overline{1}]$ , is reported. The primary geometry around the Pd^II atom closely resembles square planar (τ₄′ = 0.069). In the (E)-1-(thiophen-2-yl)-N-(p-tolyl)methanimine ligand, the phenyl and thiophene rings are not coplanar, subtending a dihedral angle of 38.5 (1)° because of steric effects. The PdCl₂N₂ coordination plane is almost perpendicular to the planes of the coordinated o-toluidine and the NC₂ fragment [dihedral angles of 84.7 (1) and 72.50 (4)°, respectively]. The Pd—NH₂ length of 2.040 (2) Å is slightly shorter than the observed mean value for other complexes involving a Pd atom attached to the nitrogen of an aniline derivative. The molecules display an interesting supramolecular synthon based on reciprocal intermolecular N–H⋯Cl hydrogen-bonding interactions of the p-toluidine amine fragment, which results in centrosymmetric dimeric units. These units are further linked by C—H⋯Cl interactions, resulting in chains in the c-axis direction where the mean-planes of the repeating fragment are oriented in the (110) plane.

Keywords: crystal structure; palladium mono-amine complex; p-toluidine; fingerprint plots.

CCDC reference: 2171669

1. Chemical context

The chemistry of monodentate mono-amine Pd^II compounds with amine ligands is of interest because the hydrogen bond between the amine and the catalyst plays a key role in the catalytic transformation of simple, easily accessible amines into highly substituted, biologically important amine-containing molecules and pharmaceutical agents (Calleja et al., 2015 ). While mono-amine Pd^II complexes are generally unstable and are formed as intermediates during the reaction, the corresponding bis(amine) Pd^II complex is stable and ultimately hampers the utility of these compounds in the C—H activation reaction. Probably because of this, well-characterized mono-amine Pd^II complexes are relatively rare. In this article we report a well-characterized and room-temperature-stable mono-amine Pd^II complex.

2. Structural commentary

In the Schiff base ligand HL1 used [HL¹ = (E)-1-(thiophen-2-yl)-N-(p-tolyl)methanimine and L² = p-toluidine], we expected that the ortho proton of the tolyl ring of HL¹ could be acidic and thus could be employed for a metallation reaction. Ding and coworkers (Ding et al., 1992 ) have reported a series of mercuration reactions on similar Schiff base ligands through electrophilic substitution reactions. On the basis of these observations, we also envisaged that a palladation reaction should take place at the ortho position of the tolyl ring in the Schiff base ligand. To investigate this C—H activation step, we attempted to prepare the complex PdL¹L²Cl. However, when we treated 2-thiophenecarboxaldehyde with two equivalents of p-toluidine in the presence of Na₂PdCl₄ in ethanol solvent at 343 K, none of the expected palladated molecules, PdL¹Cl or PdL¹L²Cl were observed, and instead we directly isolated the corresponding mono-amine Pd^II complex Pd(HL¹)L²Cl₂,1, as red needles in good yield along with a small amount of a yellow solid. The isolated solid was not soluble in common organic solvents. The filtrate of the reaction mixture was allowed to evaporate at room temperature and afforded red needles of a mono-amine Pd^II complex. In the FTIR spectra, the C=N stretching frequency in the Pd complex shifts to lower values (1611 cm⁻¹) with somewhat weaker intensity in comparison to those of the corresponding free ligand (1615 cm⁻¹). Two singlets were also observed at 3777 and 3696 cm⁻¹ for the asymmetric and symmetric N—H stretching frequencies, respectively, in the Pd complex. Both frequencies shift to longer wavelengths with weaker intensity in comparison to free p-toluidine (3421 and 3338 cm⁻¹ for N—H) as a result of the presence of strong N—H⋯Cl hydrogen-bonding interactions. This observation was further supported by single-crystal X-ray studies.

Not only does this result contrast with those found for other Schiff base compounds (Dubey et al., 2019 ), which readily form a stable palladated complex, but this reaction is also a relatively rare example of a mono-amine Pd^II complex. A search of the Cambridge Structural Database (CSD, version 5.43, update of November 2021; Groom et al., 2016 ) for structures containing a Pd(NH₂-phenyl derivative)Cl₂ fragment gave 51 hits, of which 30 were bis(amine)PdCl₂ moieties and among these was the complex Pd(p-toluidine)₂Cl₂ (YOYWOB; Tay, 2019 ) which is relevant for comparison with the title compound. Of the remaining 21, 11 contained the NH₂ group as part of a chelate ring and only 10 contained a monodentate mono-amine PdCl₂ complex (BOCTIX, Hadzovic et al., 2008 ; HIPDEP, Vicente et al., 1998 ; KASNAU, Asma et al., 2005 ; OCATEV, OCATIZ, Xia et al., 2021 ; OCEPOE, Asma & Kaminsky, 2017 ; XEKFEZ, Randell et al., 2006 ; XIYLOG, Liu et al., 2002 ; XORVIM, Hu et al., 2019 ; and YELMOS, Asma et al., 2006 ). One of these structures (HIPDEP; Vicente et al., 1998) is particularly relevant as it contains an sp² C donor attached to a PdCl₂(o-toluidine) fragment where the major difference with the present structure is the substitution of the sp² C for sp² N.

An ORTEP view of the molecular structure of Pd(HL¹)L²Cl₂, 1, is shown in Fig. 1 and selected bond lengths and bond angles are given in Table 1. This mono-amine Pd^II complex crystallizes in the triclinic space group, P $[\overline{1}]$ . The primary geometry around the Pd^II atom closely resembles square planar (τ₄′ = 0.069, where 0 = square planar and 1 = tetrahedral; Okuniewski et al., 2015 ). In the (E)-1-(thiophen-2-yl)-N-(p-tolyl)methanimine ligand, the phenyl and thiophene rings are not coplanar because of the steric clash of the hydrogen atoms attached to C5 and C7, exhibiting a dihedral angle of 38.5 (1)°. In addition, the coordination plane (Pd1, Cl1, Cl2, N1, and N2) is almost perpendicular to both the planes of the coordinated o-toluidine ring and the C5, C6, N1 fragment [dihedral angles of 84.7 (1) and 72.50 (4)°, respectively]. A search of the CSD (Groom et al., 2016) for structures containing a Pd(NH₂-phenyl derivative)Cl₂ fragment contained 90 observations of the Pd—NH₂ bond with a mean value of 2.065 (35) Å and minimum and maximum values of 2.028 Å (Baldovino-Pantaleón et al., 2007 ) and 2.171 Å (Asma et al., 2005), respectively. Thus, the length of 2.040 (2) Å in the title compound is slightly shorter than the observed mean value.

Table 1
Selected geometric parameters (Å, °)

Pd1—N1	2.015 (2)	Pd1—Cl2	2.3082 (7)
Pd1—N2	2.040 (2)	S1—C1	1.702 (3)
Pd1—Cl1	2.3067 (7)	S1—C4	1.721 (3)

N1—Pd1—N2	176.02 (9)	N2—Pd1—Cl2	91.00 (7)
N1—Pd1—Cl1	90.55 (6)	Cl1—Pd1—Cl2	174.53 (2)
N2—Pd1—Cl1	86.64 (7)	C1—S1—C4	91.29 (14)
N1—Pd1—Cl2	92.04 (6)

Figure 1
Molecular structure of Pd(HL¹)L²Cl₂ showing the atom-numbering scheme. Atomic displacement parameters are at the 30% probability level.

A related structure (HIPDEP; Vicente et al., 1998) contains an sp² C donor attached to a PdCl₂(o-toluidine) fragment where the major differences with the present structure are the substitution of the sp² C atom for sp² N, and the fact that there are cis Cl donors, which leads to a substantial trans effect involving the Pd—Cl distances. In this structure, the Pd—NH₂ distance is 2.076 (2) Å. The other related structure (Tay, 2019) is trans-Pd(o-toluidine)₂Cl₂ in which the Pd—NH₂ distance is 2.050 (3) Å.

3. Supramolecular features

The molecules display an interesting supramolecular synthon in the crystal. This synthon is based on reciprocal intermolecular N—H⋯Cl hydrogen-bonding interactions (Table 2) of the p-toluidine amine fragment and results in centrosymmetric dimeric units (Fig. 2). These units are further linked by intermolecular C—H⋯Cl interactions, resulting in chains in the c-axis direction where the mean-planes of the repeating fragment are oriented in the (110) plane.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯Cl2ⁱ	0.85 (2)	2.45 (2)	3.273 (2)	163 (2)
C2—H2A⋯Cl1ⁱⁱ	0.95	2.97	3.779 (3)	144
C5—H5A⋯Cl1ⁱⁱⁱ	0.95	2.98	3.759 (3)	140
C7—H7A⋯Cl1ⁱⁱⁱ	0.95	2.80	3.629 (3)	147
C11—H11A⋯Cl2	0.95	2.96	3.711 (3)	137
Symmetry codes: (i) ; (ii) x+1, y, z; (iii) .

Figure 2
Packing diagram for Pd(HL¹)L²Cl₂ showing the intermolecular N—H⋯Cl hydrogen-bonding interactions of the p-toluidine amine fragment resulting in centrosymmetric dimeric units that are further linked by intermolecular C—H⋯Cl interactions, resulting in chains in the c-axis direction where the mean planes of the repeating fragment are oriented in the (110) plane.

4. Synthesis and crystallization

A solution of 2-thiophenecarboxaldehyde (0.50 ml, 5 mmol) and 2 equivalent of p-toluidine (1.07 g, 10 mmol) in 20 ml of freshly distilled ethanol was allowed to stir at room temperature for 1 h. Then Na₂PdCl₄ (1.47 g, 10 mmol) was added. The reaction mixture was refluxed under stirring at 343 K for 2 h. A small amount of yellow solid gradually separated during the reaction. After stirring for 3 h the solid was filtered off and the filtrate underwent slow evaporation at room temperature to give red needles of (p-CH₃C₆H₄NH₂)SbHPdCl₂; yield: 0.80 g, 33%, m.p. 533 K. FT–IR (KBr disk, cm⁻¹): 3777 (NH), 3696 (NH), 3406, 2921, 2857, 1611 (CH=N), 1384, 1056, 754. Analysis calculated for C₁₉H₂₀N₂Cl₂PdS: C, 46.98; H, 4.15; N, 5.77. Found: C, 47.10; H, 4.30; N, 6.00%.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All hydrogen atoms were fixed geometrically with their U_iso values set to 1.2 times that of the phenyl carbons and 1.5 times that of the methyl group. The hydrogen atoms attached to nitrogen were refined isotropically.

Table 3
Experimental details

Crystal data
Chemical formula	[PdCl₂(C₇H₉N)(C₁₂H₁₁NS)]
M_r	485.73
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.2135 (4), 9.4060 (4), 12.9032 (5)
α, β, γ (°)	79.866 (2), 70.000 (2), 67.753 (2)
V (Å³)	971.17 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.34
Crystal size (mm)	0.21 × 0.16 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.622, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	22977, 7379, 5166
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.771

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.090, 1.04
No. of reflections	7379
No. of parameters	236
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.75, −1.05
Computer programs: APEX2 (Bruker, 2005 ), SAINT (Bruker, 2002 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2171669

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022004960/tx2049sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022004960/tx2049Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Dichlorido(4-methylaniline-κN)[N-(4-methylphenyl)-1-(thiophen-2-yl)methanimine-κN]palladium(II) top

Crystal data top

[PdCl₂(C₇H₉N)(C₁₂H₁₁NS)]	Z = 2
M_r = 485.73	F(000) = 488
Triclinic, P1	D_x = 1.661 Mg m⁻³
a = 9.2135 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4060 (4) Å	Cell parameters from 7754 reflections
c = 12.9032 (5) Å	θ = 2.6–31.6°
α = 79.866 (2)°	µ = 1.34 mm⁻¹
β = 70.000 (2)°	T = 100 K
γ = 67.753 (2)°	Prism, red-orange
V = 971.17 (7) Å³	0.21 × 0.16 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	5166 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.074
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 33.2°, θ_min = 2.6°
T_min = 0.622, T_max = 0.747	h = −14→14
22977 measured reflections	k = −14→14
7379 independent reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: mixed
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0211P)² + 0.1526P] where P = (F_o² + 2F_c²)/3
7379 reflections	(Δ/σ)_max = 0.001
236 parameters	Δρ_max = 0.75 e Å⁻³
3 restraints	Δρ_min = −1.04 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pd1	0.53572 (2)	0.53405 (2)	0.70240 (2)	0.01680 (6)
Cl1	0.33922 (8)	0.70208 (8)	0.83363 (6)	0.02463 (14)
Cl2	0.71210 (8)	0.36598 (7)	0.56567 (5)	0.02350 (14)
S1	0.85995 (9)	0.55990 (9)	0.70536 (6)	0.02886 (16)
N1	0.6002 (3)	0.3778 (2)	0.82190 (18)	0.0176 (4)
N2	0.4704 (3)	0.7036 (3)	0.5873 (2)	0.0220 (5)
H2N1	0.377 (3)	0.770 (3)	0.622 (2)	0.032 (9)*
H2N2	0.444 (3)	0.674 (3)	0.5400 (19)	0.028 (9)*
C1	1.0173 (4)	0.5879 (3)	0.7297 (3)	0.0305 (7)
H1A	1.076419	0.650381	0.682505	0.037*
C2	1.0496 (3)	0.5118 (3)	0.8234 (3)	0.0298 (7)
H2A	1.133321	0.516183	0.848589	0.036*
C3	0.9467 (3)	0.4256 (3)	0.8798 (2)	0.0198 (5)
H3A	0.952608	0.364962	0.946424	0.024*
C4	0.8334 (3)	0.4419 (3)	0.8232 (2)	0.0197 (5)
C5	0.7160 (3)	0.3650 (3)	0.8615 (2)	0.0198 (5)
H5A	0.724011	0.295542	0.924122	0.024*
C6	0.4938 (3)	0.2900 (3)	0.8769 (2)	0.0192 (5)
C7	0.4335 (3)	0.2799 (3)	0.9911 (2)	0.0227 (6)
H7A	0.463677	0.329462	1.034377	0.027*
C8	0.3296 (3)	0.1977 (3)	1.0415 (2)	0.0238 (6)
H8A	0.288941	0.191174	1.119823	0.029*
C9	0.2829 (3)	0.1243 (3)	0.9811 (2)	0.0225 (6)
C10	0.3476 (3)	0.1323 (3)	0.8664 (2)	0.0258 (6)
H10A	0.320210	0.079781	0.823403	0.031*
C11	0.4510 (3)	0.2156 (3)	0.8141 (2)	0.0240 (6)
H11A	0.492453	0.221808	0.735826	0.029*
C12	0.1631 (3)	0.0410 (3)	1.0382 (3)	0.0301 (7)
H12A	0.190105	−0.017694	1.103815	0.045*
H12B	0.169958	−0.029332	0.987540	0.045*
H12C	0.051154	0.115955	1.060209	0.045*
C13	0.5932 (3)	0.7750 (3)	0.5331 (2)	0.0198 (5)
C14	0.6077 (3)	0.8804 (3)	0.5877 (2)	0.0223 (6)
H14A	0.539342	0.903607	0.661152	0.027*
C15	0.7222 (3)	0.9519 (3)	0.5351 (2)	0.0240 (6)
H15A	0.731007	1.025059	0.572709	0.029*
C16	0.8240 (3)	0.9187 (3)	0.4286 (2)	0.0257 (6)
C17	0.8092 (4)	0.8100 (3)	0.3760 (2)	0.0287 (6)
H17A	0.878381	0.785164	0.303024	0.034*
C18	0.6952 (3)	0.7373 (3)	0.4283 (2)	0.0253 (6)
H18A	0.687823	0.661983	0.391948	0.030*
C19	0.9476 (4)	0.9977 (4)	0.3690 (3)	0.0348 (7)
H19A	0.938923	1.073179	0.416289	0.052*
H19B	0.925215	1.050022	0.300474	0.052*
H19C	1.058806	0.921028	0.351413	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01898 (10)	0.01641 (10)	0.01739 (10)	−0.00721 (7)	−0.00816 (8)	0.00119 (7)
Cl1	0.0253 (3)	0.0249 (3)	0.0226 (3)	−0.0071 (3)	−0.0069 (3)	−0.0032 (3)
Cl2	0.0275 (3)	0.0217 (3)	0.0215 (3)	−0.0066 (3)	−0.0086 (3)	−0.0033 (2)
S1	0.0309 (4)	0.0297 (4)	0.0300 (4)	−0.0159 (3)	−0.0113 (3)	0.0054 (3)
N1	0.0217 (11)	0.0162 (10)	0.0173 (11)	−0.0082 (9)	−0.0082 (9)	0.0017 (8)
N2	0.0245 (12)	0.0213 (12)	0.0232 (13)	−0.0078 (10)	−0.0127 (11)	0.0022 (9)
C1	0.0253 (15)	0.0279 (15)	0.0389 (18)	−0.0150 (12)	−0.0021 (14)	−0.0050 (13)
C2	0.0245 (15)	0.0322 (16)	0.0368 (18)	−0.0118 (12)	−0.0078 (14)	−0.0103 (13)
C3	0.0145 (12)	0.0182 (12)	0.0269 (14)	−0.0071 (10)	−0.0031 (11)	−0.0047 (10)
C4	0.0219 (13)	0.0195 (12)	0.0178 (13)	−0.0081 (10)	−0.0056 (11)	0.0005 (10)
C5	0.0224 (13)	0.0167 (12)	0.0198 (13)	−0.0055 (10)	−0.0075 (11)	−0.0003 (10)
C6	0.0196 (13)	0.0165 (12)	0.0222 (14)	−0.0061 (10)	−0.0089 (11)	0.0022 (10)
C7	0.0232 (14)	0.0246 (14)	0.0227 (14)	−0.0104 (11)	−0.0066 (12)	−0.0026 (11)
C8	0.0229 (14)	0.0250 (14)	0.0215 (14)	−0.0082 (11)	−0.0035 (12)	−0.0024 (11)
C9	0.0189 (13)	0.0171 (12)	0.0296 (15)	−0.0052 (10)	−0.0069 (12)	0.0002 (11)
C10	0.0300 (15)	0.0237 (14)	0.0287 (16)	−0.0128 (12)	−0.0105 (13)	−0.0021 (11)
C11	0.0280 (15)	0.0282 (14)	0.0194 (14)	−0.0127 (12)	−0.0092 (12)	0.0007 (11)
C12	0.0258 (15)	0.0242 (14)	0.0398 (18)	−0.0128 (12)	−0.0059 (14)	0.0010 (13)
C13	0.0224 (13)	0.0169 (12)	0.0200 (13)	−0.0059 (10)	−0.0096 (11)	0.0034 (10)
C14	0.0253 (14)	0.0191 (13)	0.0202 (14)	−0.0061 (11)	−0.0068 (12)	0.0013 (10)
C15	0.0293 (15)	0.0194 (13)	0.0265 (15)	−0.0089 (11)	−0.0127 (13)	0.0011 (11)
C16	0.0211 (13)	0.0239 (14)	0.0301 (16)	−0.0059 (11)	−0.0118 (13)	0.0075 (11)
C17	0.0262 (15)	0.0281 (15)	0.0234 (15)	−0.0030 (12)	−0.0036 (13)	−0.0030 (12)
C18	0.0314 (15)	0.0232 (14)	0.0210 (14)	−0.0081 (12)	−0.0080 (13)	−0.0029 (11)
C19	0.0290 (16)	0.0328 (17)	0.0409 (19)	−0.0140 (13)	−0.0093 (15)	0.0073 (14)

Geometric parameters (Å, º) top

Pd1—N1	2.015 (2)	C8—H8A	0.9500
Pd1—N2	2.040 (2)	C9—C10	1.394 (4)
Pd1—Cl1	2.3067 (7)	C9—C12	1.507 (4)
Pd1—Cl2	2.3082 (7)	C10—C11	1.384 (4)
S1—C1	1.702 (3)	C10—H10A	0.9500
S1—C4	1.721 (3)	C11—H11A	0.9500
N1—C5	1.291 (3)	C12—H12A	0.9800
N1—C6	1.442 (3)	C12—H12B	0.9800
N2—C13	1.446 (3)	C12—H12C	0.9800
N2—H2N1	0.868 (16)	C13—C18	1.372 (4)
N2—H2N2	0.848 (16)	C13—C14	1.382 (4)
C1—C2	1.358 (4)	C14—C15	1.383 (4)
C1—H1A	0.9500	C14—H14A	0.9500
C2—C3	1.410 (4)	C15—C16	1.384 (4)
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.417 (4)	C16—C17	1.392 (4)
C3—H3A	0.9500	C16—C19	1.509 (4)
C4—C5	1.429 (3)	C17—C18	1.386 (4)
C5—H5A	0.9500	C17—H17A	0.9500
C6—C7	1.386 (4)	C18—H18A	0.9500
C6—C11	1.388 (4)	C19—H19A	0.9800
C7—C8	1.376 (4)	C19—H19B	0.9800
C7—H7A	0.9500	C19—H19C	0.9800
C8—C9	1.383 (4)

N1—Pd1—N2	176.02 (9)	C8—C9—C10	118.0 (2)
N1—Pd1—Cl1	90.55 (6)	C8—C9—C12	120.7 (3)
N2—Pd1—Cl1	86.64 (7)	C10—C9—C12	121.3 (3)
N1—Pd1—Cl2	92.04 (6)	C11—C10—C9	121.1 (3)
N2—Pd1—Cl2	91.00 (7)	C11—C10—H10A	119.5
Cl1—Pd1—Cl2	174.53 (2)	C9—C10—H10A	119.5
C1—S1—C4	91.29 (14)	C10—C11—C6	119.6 (3)
C5—N1—C6	118.0 (2)	C10—C11—H11A	120.2
C5—N1—Pd1	124.71 (18)	C6—C11—H11A	120.2
C6—N1—Pd1	116.66 (15)	C9—C12—H12A	109.5
C13—N2—Pd1	113.09 (16)	C9—C12—H12B	109.5
C13—N2—H2N1	112 (2)	H12A—C12—H12B	109.5
Pd1—N2—H2N1	106 (2)	C9—C12—H12C	109.5
C13—N2—H2N2	110 (2)	H12A—C12—H12C	109.5
Pd1—N2—H2N2	113 (2)	H12B—C12—H12C	109.5
H2N1—N2—H2N2	102 (2)	C18—C13—C14	120.4 (3)
C2—C1—S1	113.1 (2)	C18—C13—N2	120.1 (2)
C2—C1—H1A	123.4	C14—C13—N2	119.5 (2)
S1—C1—H1A	123.4	C13—C14—C15	119.7 (3)
C1—C2—C3	113.4 (3)	C13—C14—H14A	120.1
C1—C2—H2A	123.3	C15—C14—H14A	120.1
C3—C2—H2A	123.3	C14—C15—C16	121.1 (3)
C2—C3—C4	110.5 (2)	C14—C15—H15A	119.4
C2—C3—H3A	124.7	C16—C15—H15A	119.4
C4—C3—H3A	124.7	C15—C16—C17	118.1 (3)
C3—C4—C5	122.3 (2)	C15—C16—C19	121.9 (3)
C3—C4—S1	111.66 (19)	C17—C16—C19	120.0 (3)
C5—C4—S1	126.0 (2)	C18—C17—C16	121.2 (3)
N1—C5—C4	128.2 (2)	C18—C17—H17A	119.4
N1—C5—H5A	115.9	C16—C17—H17A	119.4
C4—C5—H5A	115.9	C13—C18—C17	119.5 (3)
C7—C6—C11	119.9 (2)	C13—C18—H18A	120.3
C7—C6—N1	120.8 (2)	C17—C18—H18A	120.3
C11—C6—N1	119.3 (2)	C16—C19—H19A	109.5
C8—C7—C6	119.6 (3)	C16—C19—H19B	109.5
C8—C7—H7A	120.2	H19A—C19—H19B	109.5
C6—C7—H7A	120.2	C16—C19—H19C	109.5
C7—C8—C9	121.8 (3)	H19A—C19—H19C	109.5
C7—C8—H8A	119.1	H19B—C19—H19C	109.5
C9—C8—H8A	119.1

C4—S1—C1—C2	−0.2 (3)	C7—C8—C9—C12	−177.2 (2)
S1—C1—C2—C3	0.4 (3)	C8—C9—C10—C11	−2.2 (4)
C1—C2—C3—C4	−0.4 (3)	C12—C9—C10—C11	176.6 (3)
C2—C3—C4—C5	179.1 (2)	C9—C10—C11—C6	1.2 (4)
C2—C3—C4—S1	0.3 (3)	C7—C6—C11—C10	0.3 (4)
C1—S1—C4—C3	−0.1 (2)	N1—C6—C11—C10	−179.4 (2)
C1—S1—C4—C5	−178.9 (3)	Pd1—N2—C13—C18	102.6 (2)
C6—N1—C5—C4	−178.6 (2)	Pd1—N2—C13—C14	−76.9 (3)
Pd1—N1—C5—C4	−7.9 (4)	C18—C13—C14—C15	2.1 (4)
C3—C4—C5—N1	175.2 (3)	N2—C13—C14—C15	−178.3 (2)
S1—C4—C5—N1	−6.2 (4)	C13—C14—C15—C16	−0.6 (4)
C5—N1—C6—C7	43.1 (3)	C14—C15—C16—C17	−0.6 (4)
Pd1—N1—C6—C7	−128.3 (2)	C14—C15—C16—C19	178.9 (2)
C5—N1—C6—C11	−137.2 (3)	C15—C16—C17—C18	0.3 (4)
Pd1—N1—C6—C11	51.4 (3)	C19—C16—C17—C18	−179.1 (3)
C11—C6—C7—C8	−0.9 (4)	C14—C13—C18—C17	−2.4 (4)
N1—C6—C7—C8	178.8 (2)	N2—C13—C18—C17	178.1 (2)
C6—C7—C8—C9	−0.1 (4)	C16—C17—C18—C13	1.1 (4)
C7—C8—C9—C10	1.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···Cl2ⁱ	0.85 (2)	2.45 (2)	3.273 (2)	163 (2)
C2—H2A···Cl1ⁱⁱ	0.95	2.97	3.779 (3)	144
C5—H5A···Cl1ⁱⁱⁱ	0.95	2.98	3.759 (3)	140
C7—H7A···Cl1ⁱⁱⁱ	0.95	2.80	3.629 (3)	147
C11—H11A···Cl2	0.95	2.96	3.711 (3)	137

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+2.

Acknowledgements

PS is obliged to the Science and Engineering Research Board, New Delhi, India, for a Teacher Associateship for Research Excellence research grant (Project No. TAR/2021/000075). The authors are grateful to Central Drug Research Institute Lucknow for recording the analytical data.

Funding information

Funding for this research was provided by: Science and Engineering Research Board (award No. SB/FT/CS-036/2012).

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